The possibility of exploiting a thermally-induced solid-state reaction to obtain the formation of a fluorene and TCNQ molecular complex was proposed by some of us (Kumar et al., Cryst. Growth Des., 2009, 9(8), 3396–3404). In this paper, we generalize and rationalize the approach to other charge transfer (CT) molecular complexes with naphthalene and anthracene, changing the size of the donor moiety to propose a general approach for the preparation of this class of materials by exploiting the solid-state synthesis method. Moreover, the kinetic features of the solid state reactions were fully elucidated by Raman spectroscopy and high resolution X-ray Powder Diffraction analysis (in situ Raman/XRPD), exploiting the Avrami equation in isothermal and non-isothermal conditions; rate constants, reaction orders and activation energies were obtained. All the three tested solid-state charge transfer (SS-CT) reactions obeyed a general rule, whereby the most apt reaction temperature was predicted. Finally, a method based on principal component analysis (PCA) for a fast kinetic analysis of in situ XRD synchrotron data was successfully developed, employing a formalism suitable for the analysis of non-isothermal reaction data, thus allowing a high throughput approach for the fast screening of the kinetics of parent reactions. PCA analysis was exploited as an alternative technique to obtain kinetic information in a faster and more efficient way, which can be used for online monitoring and/or in all those cases where Rietveld analysis is not feasible.